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Fine Control of the Redox Reactivity of a Nonheme Iron( III)-Peroxo Complex by Binding Redox-Inactive Metal Ions
- Title
- Fine Control of the Redox Reactivity of a Nonheme Iron( III)-Peroxo Complex by Binding Redox-Inactive Metal Ions
- Authors
- Bae, Seong Hee; Lee, Yong-Min; Fukuzumi, Shunichi; Nam, Wonwoo
- Ewha Authors
- 남원우; Shunichi Fukuzumi; 이용민
- SCOPUS Author ID
- 남원우; Shunichi Fukuzumi; 이용민
- Issue Date
- 2017
- Journal Title
- ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
- ISSN
- 1433-7851
1521-3773
- Citation
- ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol. 56, no. 3, pp. 801 - 805
- Keywords
- iron-peroxo intermediates; Lewis acidity; nonheme iron enzymes; reactive species; redox-inactive metal ions
- Publisher
- WILEY-V C H VERLAG GMBH
- Indexed
- SCIE; SCOPUS
- Document Type
- Article
- Abstract
- Redox-inactive metal ions are one of the most important co-factors involved in dioxygen activation and formation reactions by metalloenzymes. In this study, we have shown that the logarithm of the rate constants of electron-transfer and C-H bond activation reactions by nonheme iron(III)-peroxo complexes binding redox-inactive metal ions, [(TMC)Fe-III(O-2)](+)-Mn+ (Mn+=Sc3+, Y3+, Lu3+, and La3+), increases linearly with the increase of the Lewis acidity of the redox-inactive metal ions (Delta E), which is determined from the g(zz) values of EPR spectra of O-2(center dot-)-Mn+ complexes. In contrast, the logarithm of the rate constants of the [(TMC)Fe-III(O-2)](+)-Mn+ complexes in nucleophilic reactions with aldehydes decreases linearly as the Delta E value increases. Thus, the Lewis acidity of the redox-inactive metal ions bound to the mononuclear nonheme iron(III)-peroxo complex modulates the reactivity of the [(TMC)Fe-III(O-2)](+)-Mn+ complexes in electron-transfer, electrophilic, and nucleophilic reactions.
- DOI
- 10.1002/anie.201610828
- Appears in Collections:
- 자연과학대학 > 화학·나노과학전공 > Journal papers
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